Chromium tris-diorgano-orthophosphates and their preparation

ABSTRACT

This invention comprises novel chromium tris-diorganoorthophosphates, including coordination polymers thereof, and their preparation by the reaction of certain simple salts or esters of trivalent chromium with alkali or alkaline earth metal salts of diorgano orthophosphoric acid and separation of the novel compounds. The simple salts or esters include primarily the halides, nitrates, sulfates and acetates of trivalent chromium. The alkali metal salts or alkaline earth metal salts of diorgano orthophosphoric acids include primarily compounds of the general formula M&#39;&#39; (OP(O)(OR)2)n in which M&#39;&#39; is an alkali metal or an alkaline earth metal, each n is the valence of such metal and each R can be an alkyl, alkoxyalkyl or cycloalkyl group of one to about eight carbon atoms and the chlorinated and brominated derivatives thereof. This invention also comprises the use of these novel compounds in conjunction with alkyl aluminum halides as catalysts for alkylation of benzene and other aromatic compounds and the polymerization of ethylene, propylene and other olefins.

[22] Filed:

Meyer [11] 3,907,849 [451 Sept. 23, 1975 CHROMIUMTRIS-DIORGANO-ORTI-IOPIIOSPHATES AND THEIR PREPARATION Jeffrey G. Meyer,Adrian, Mich.

[731 Assignee: Anderson Development Company,

Adrian, Mich.

Dec. 29, 1972 [21] Appl. No.: 319,621

[75] Inventor:

[52] U.S. Cl 260/438.5 R; 252/431 P; 260/2 M;

260/668 B; 260/671 C [51] Int. Cl. C07F 11/00 [58] Field of Search260/438.5 R

[56] References Cited UNITED STATES PATENTS OTHER PUBLICATIONS ChemicalAbstracts, Vol. 71, 9246b (1969).

Inorganic Chemistry, Vol. 9, No. 9, 2053-2058 Primary Examinerl-lelen M.S. Sneed [57] ABSTRACT This invention comprises novel chromiumtris-diorgano-orthophosphates, including coordination polymers thereof,and their preparation by the reaction of certain simple salts or estersof trivalent chromium with alkali or alkaline earth metal salts ofdiorgano orthophosphoric acid and separation of the novel compounds. Thesimple salts or esters include primarily the halides, nitrates, sulfatesand acetates of trivalent chromium. The alkali metal salts or alkalineearth metal salts of diorgano orthophosphoric acids include primarilycompounds of the general formula M [OP- (O)(OR) in which M is an alkalimetal or an alkaline earth metal, each n is the valence of such metaland each R can be an alkyl, alkoxyalkyl or cycloalkyl group of one toabout eight carbon atoms and the chlorinated and brominated derivativesthereof.

This invention also comprises the use of these novel compounds inconjunction with alkyl aluminum halides as catalysts for alkylation ofbenzene and other aromatic compounds and the polymerization of ethylene,propylene and other olefins.

7 Claims, No Drawings CHROMIUM TRIS-DIORGANO-ORTI-IOPIIOSPHATES ANDTHEIR PREPARATION BACKGROUND OF THE INVENTION A number of systems havebeen devised for the preparation of numerous types of organophosphoruscompounds containing at least one other type of metal. Some of thesesystems are illustrated in US. Pat. Nos. 2,228,659; 2,370,080;2,488,662; 2,885,417; 3,055,925; 3,065,065; 3,231,347; 3,275,668;3,297,573; 3,334,978; 3,354,189 and 3,412,182 and United KingdomSpecification No. 1,135,261. These systems generally employ solventsand/or phosphorus compounds containing at least one acidic hydrogenatom.

It is a principal object of this invention to provide a novel class ofchromium organophosphorus compounds and novel methods of preparing suchorganophosphorus compounds. It is a further object of this invention toprovide a method for preparing chromium organophosphorus compoundssoluble in organic sol vents from known salts of organicorthophosphates.

Alkyl aromatics are known to be prepared by the reaction of aromatichydrocarbons with olefins in the presence of catalyst mixtures of alkylaluminum halides and heavy metal halides as set forth in US. Pat. Nos.3,129,255; 3,129,256 and 3,134,822. High molecular weight polymers andcopolymers of olefins are known to be prepared in the presence ofvanadium oxy diethyl phosphate as set forth in US. Pat. Nos. 3,595,843and 3,595,844.

Another object of this invention is to provide a new catalystcombination for such alkylation and polymerization. A further object ofthis invention is to provide a method for activating this catalystcomposition.

SUMMARY OF THE INVENTION This invention comprises novel compounds of thegeneral formula in which each R is a non-aromatic hydrocarbon group freeof aliphatic unsaturation, i.e. an alkyl or cycloalkyl group, containingone to eight, preferably two to four, carbon atoms or a non-aromatichydrocarbon ether group free of aliphatic unsaturation, i.e., analkoxyalkyl group, containing three to six carbon atoms or a chlorinatedor brominated derivative of any of such groups. These compounds can bemonomers or coordination polymers or both.

This invention also comprises the method of preparing said compoundswherein l a metal salt of formula M'[OP (OR) in which M is an alkalimetal or alkaline earth metal, 11 is the valence of the element M andeach R is as defined above is reacted with a chromium compound of theformula M,,Z,, in which each M is trivalent chromium, each Z is anon-reducing substitucnt selected from the group consisting of anions ofnon-metallic inorganic acids, the hydroxyl group and organic carboxylicgroups of from one to about 18 carbon atoms, u is 1 or 2, b is 1 or 3and the values of a and I) depend on the valence ofZ and (2) theresulting chromium organophosphate is extracted from the reactionproduct by a solvent in which the M'-containing by-product is notsoluble.

This invention also comprises a combination catalyst for olefinpolymerization and for alkylation of aromatic hydrocarbons with olefins,said catalyst consisting essentially of the reaction product of (A) achromium tris-diorgano-orthophosphate of the general formula Cr [OP (0)(OR) in which each R is as defined above and (B) an alkyl aluminumhalide of the general formula R,. Al X,, in which each R is an alkylgroup of one to six carbon atoms, each X is a halogen atom, preferablychlorine or bromine, each of c and a is l or 2 and the total of c and dis 3. The mol ratio of (A) to (B) can range from 1:1 to 1:20 but ispreferably in the range of 1:8 to 1:12 unlike the ratios set forth inthe above-noted U.S. patents relating to alkylation.

This invention further comprises the use of the above-described catalystcombination in a method for polymerization and/or alkylation consistingessentially of l) mixing the catalyst combination of (A) and (B)described above with (C) a monoor di-olefin which can be any aliphatic,cycloaliphatic or aromatic hydrocarbon preferably containing no morethan about 20 carbon atoms, more preferably no more than about 12 carbonatoms, either alone or with (D) an aromatic hydrocarbon containing fromsix to 14 aromatic carbon atoms and, optionally, substituted with up toabout four lower alkyl groups or other non-interfering substituents suchas, for example, oxygen-free anions of nonmetallic inorganic acids suchas chlorine atoms, bromine atoms and nitrile groups at a temperature andpressure and for a time sufficient to cause reaction of (C), alone orwith (D), and (2) separating the resulting product. The total amount of(A) and (B) is present in an amount of from about 0.0001 to 0.01 totalmol per mol of combined (C) and (D). The ratio of (C) to (D) depends onwhether the primary end-product is an alkylated aromatic compound or apolymerized olefin. This system operates spontaneously as soon as thecomponents are mixed. Generally, the system temperature can range from 0to 250C, preferably 50 to 150C., and the system pressure can range from1 to 500 psig., preferably 10 to psig. The desired reaction can takefrom 1 minute to 24 hours, but the reaction generally takes from 5minutes to 2 hours.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel compounds of thisinvention have the general unit formula Cr [OP (0) (OR) either monomersor polymers thereof, principally coordination polymers, composedpreferably of from one to ten units, and are preferably prepared by (1)mixing the metal salt and chromium compounds defined above at atemperature between about 30 and 100C. and at a pressure and for a timesufficient to cause a reaction between them to produce a product of thisinvention and 2) separating the desired product from the reactionmixture. This reaction follows the general course:

Each R can be, for example, any alkyl, alkyoxyalkyl or cycloalkyl groupof up to about eight carbon atoms.

Specific examples of such groups include methyl, ethyl,

propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl,hexyl, isohexyl, 2,2,4-trimethylpentyl, 2- methylpentyl,2,2-dimethylbutyl, 2,3-dimethylbuty], heptyl, Z-methylhexyl,3-methylhexyl, ,3,3-

dimethylpentyl, octyl, 2,3-dimethylhexyl, 2,4- dimethylhexyl,2-ethylhexyl, 2-ethylbutyl, methoxyethyl, ethoxyethyl, butoxyethyl,cyclohexyl, cyclobutyl and cyclopentyl groups and chlorinated andbrominated derivatives such as the 3-chloropropyl, chlorocyclohexyl and2,3-dibromopropyl groups.

The diorgano orthophosphate salts employed in this invention areconventional materials, and a number of diorganophosphoric acids arecommercially available. Accordingly, their preparation is not a part ofthis invention. For example, the phosphate chlorides can be prepared byreacting such materials as POCl with the desired alcohols in suchproportions, i.e.,-two mols of alcohol per mol of phosphorus in POCl asto produce the desired diorgano orthophosphate chloride Cl P (O) (OR)The corresponding diorganophosphoric acid can be prepared by hydrolyzingthe phosphate chloride. Either the acid or the chloride can be reactedwith thehydroxide of an alkali metal, such as sodiumor potassium, or analkaline earth metal, such as magnesium or calcium, to form the saltuseful for preparing the soluble form of the chromiumdiorganophosphates.

Alternatively, the alkaline earth metal salt can be prepared bydealkylating a triorgano orthophosphate at elevated temperatures with analkaline earth halide or similar salt. Thus, typical examples of theorganic phosphorus compounds which can be used in this latter method aretriorgano orthophosphates such as trimethyl orthophosphate, triethylorthophosphate, tributyl orthophosphate, dimethyl amyl orthophosphate,diethyl amyl orthophosphate, isopropyl di-isoamyl orthophosphate,tritertiary-butyl orthophosphate, tri-n-amyl orthophosphate, triisoamylorthophosphate, trihexyl orthophosphate, ethyl dihexyl orthophosphate,tri-Z- ethylhexyl orthophosphate, tri-n-octyl orthophosphate,tri-Z-ethoxyethyl orthophosphate, dimethyl n-octyl orthophosphate,diethyl n-octyl orthophosphate, di-npropyl n-octyl orthophosphate,isopropyl isoamyl isooctyl orthophosphate, tricyclohexyl orthophosphate,tricycloheptyl orthophosphate, diethyleyclobutyl orthophosphate andchloropropyl di-isopropyl orthophosphate.

Typical examples of the metal salts which can be used for preparingchromium tris-diorganoorthophosphate include sodium dimethylorthophosphate, sodium dihexyl orthophosphate, potassium di-tbutylorthophosphate, lithium dicyclohexyl orthophosphate, magnesiumbis(diethyl orthophosphate), calcium bis(dipropyl orthophosphate),strontium bis(- dibutyl orthophosphate) and the like. Generally, anymetal salt M [OP (OR);],, is used in a solvent solution.

The reaction conditions for the preferred preparation of the novelcompounds of this invention can vary considerably, but the temperaturerange is generally from about 0 to about 150C., preferably about 30 toabout 100C. The temperatures which can be used depend primarily on thestability of the products and the solubility of the reactants. Theabsolute pressure of the reaction system can range from about 0.01 toabout 1.5 atmospheres, depending on the boiling points and/or vaporpressures of the reactants, products and solvent medium, but usually thepressure of the system is at The chromium compounds used in the methodsof this invention for the preparation of the novel chromiumtris-diorgano orthophosphates of this invention are all well known inthe art. They can be best defined as selected from the group consistingof metal salts of non-reducing non-metallic inorganic acids andcarboxylic acids containing up to about 18 carbon atoms and metalhydroxides, the metal being limited to trivalent chromium and can bedescribed also as a compound of the general formula M Z in which each Mis a trivalent chromium atom. The Z substituent must be nonreducing andcan be an anion of a non-metallic inorganic acid, such as the chlorate,bromite, fluorosilicate, chloride, bromide, iodide, fluoride, nitrate,nitrite, perchlorate, silicate, sulfate and bisulfate anions, a hydroxyl group or an organic carboxylic group containing from one to about18 carbon atoms, preferably in the form of an aliphatic hydrocarbon asin a fatty acid residue. The preferable Z substituents are halogenatoms, the nitrate group, the sulfate group and fatty acid residues ofno more than about six carbon atoms.

While any of the above-described types of Z substituents can be attachedto M atoms, it is most preferable that each substituentis a chlorineatom, a nitrate group or a low molecular weight organic carboxylicgroup, preferably the acetate group. This preference is based oneconomic practicality, first, with regard to the cost of the reactantM,,Z,, and, second, with regard to the separation of the product fromthe reaction mixture. While the techniques for separation of chemicalsfrom any type of system have become very sophisticated, it is preferablethat starting components are selected so that the desired product andthe by-product automatically separate at ambient temperatures andpressures. Thus, in the preferred method, if the desired product Cr [OP(0) (OR) is insoluble in the reaction medium, it is preferable that theby-product MZ is soluble in the solvent from which the desired productwill precipitate. On the other hand, if the desired product is solublein the solvent medium, it is preferable that the by-product is not.Consequently, the choice of reactants is usually governed by a simpledetermination of the easiest way of producing and separating the desiredproduct, but it need not be.

Purification of the desired product immediately after preparation iscritical for insuring the form of material useful as a catalystcomponent. Particularly important is removal of water and polar organicimpurities which may catalyze coordination polymerization of themonomeric or coordination oligomeric composition {Cr [OP (0) (OR) toinsoluble form whereinjis larger than about 10. Addition of dryingagents, such as molecular sieves, or chemical scavengers, such as metalhydrides, to solutions containing the monomeric or oligomeric product isparticularly suitable for this purpose. I

Examples of desired products include:

Chromium tris(dipropyl orthophosphate), chromium tris(di-n-octylorthophosphate), chromium tris(di-4,4- dimethylhexyl orthophosphate),chromium tris(di-Z- ethylhexyl orthophosphate), chromium tris( diethylorthophosphate), chromium tris(diisobutyl orthophosphate), chromiumtris(monobutyl mono-tert-butyl orthophosphate), chromium tris(monopentylmono-2- methylpentyl orthophosphate), chromium tris(di- 3- methylhexylorthophosphate), chromium tris(mono-2- ethylhexyl mono-3-methylhexylorthophosphate), chromium tris(di-2,3-dimethylhexyl orthophosphate),

chromium tris(dicyclohexyl orthophosphate), chromium tris(dibutylorthophosphate), chromium bis(- diethyl orthophosphate) mono(diisohexylorthophosphate), chromium tris(di-3,3-dimethylpentyl orthophosphate),chromium bis(monoheptyl monohexyl orthophosphate) mono(monohepty1monooctyl orthophosphate), chromium tris(di-2,2,4-trimethylpentylorthophosphate), chromium tris(di-2-ethoxyethyl orthophosphate),chromium tris(dicyclopentyl orthophosphate), chromiumtris(di-2,2-dimethylbutyl orthophosphate), chromium bis(monopropylmonobutyl orthophosphate) mono (monoamyl monohexyl orthophosphate),chromium tris(dicyclohexyl orthophosphate), chromium tris(dicyclobutylorthophosphate), chromium tris(di-3-chloropropyl orthophosphate),chromium tris(bis-2,3-dibromopropyl orthophosphate and chromiumtris(di-2-chloroethyl orthophosphate).

The chromium tris-diorgano-orthophosphates of this invention areparticularly useful in combination with alkyl aluminum halides as acatalyst system for olefin polymerization and alkylation of aromatichydrocarbons. More specifically, this catalyst system consistsessentially of the reaction product of (A) one or more chromiumtris-diorgano-orthophosphates of the formula Cr [OP (OR) as describedabove and (B) one or more alkyl aluminum halides of the general forrnulaR' Al X,, in which each R is an alkyl group of one to about six carbonatoms, each X is a halogen atom, preferably chlorine or bromine, each ofc and d is l or 2 and the total of c and d is 3, the mol ratio of (A) to(B) being in the range of 1:1 to 1:20, preferably 1:8 to 1:12.

The alkyl aluminum halides are primarily the compounds R Al X R gAl Xand mixtures thereof including the mixtures of the formula R' Al Xusually referred to as the sesquihalides. Each R can be, for example, amethyl, ethyl, propyl, iso-propyl, n-butyl, secbutyl, tert-butyl, pentylor hexyl group. Each X can be fluorine, chlorine, bromine or iodine.Examples of suitable alkyl aluminum halides include diethylaluminumchloride, n-butylaluminum dibromide, ethyl aluminum sesquichloride,methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethylaluminum sesquifluoride and the like.

The catalyst composition of (A) and (B) is simply prepared by mixing thecomponents. The components there may be the desired reaction in 5minutes or less,

-it is known that the desired reaction takes place in no more than 2hours.

The combination catalyst system is used in the method comprising 1mixing the reaction product of (A) and (B) described above with (C) oneor more monoor di-olefins which can be any aliphatic, cycloaliphatic oraromatic hydrocarbons preferably contain- '-ing no more than aboutcarbon atoms, more preferaibly no more than about 12 carbon atoms, aloneor with (D) an aromatic hydrocarbon containing from six to ;about 14aromatic carbon atoms, said hydrocarbon being optionally substitutedwith up to about four lower ialkyl groups or other non-interferingsubstituents such as anions of non-metallic inorganic acids and nitrilegroups, at a temperature and pressure and for a time sufficient to causethe reaction of (C) and (2) separating the resulting product.

Examples of suitable olefins (C) include ethylene, propylene,isobutylene, butene-l, cis-butene-Z, transbutene-2, pentene-l, hexene-l,cyclopentene, cyclohexene, cycloheptene, 4-methy1cyc1ooctene, 2-methylbutene-l, pentadecene-l, styrene, butadiene, isoprene,3-vinylcyclohexene and the acyclic and cyclic terpenes. Substitution orinclusion of non-interfering groups as in acrylonitrile, methyl vinylether, vinyl chloride and chloroprene is not intended to put sucholefins outside the scope of suitable olefins (C). The aromatic olefinsare preferably limited to a maximum of 8 carbon atoms. Thecycloaliphatic and aliphatic olefins are preferably limited to a maximumof about six carbon atoms.

Examples of suitable alkylatable aromatic hydrocarbons (D) includebenzene, toluene, xylenes, chlorobenzene, dichlorobenzene, ethylbenzene,tetralin, cumene, diisopropylbenzenes, durene, naphthalene,isopropylnaphthalenes, 1,2,4-triisopropylbenzene, phenanthrene,biphenyl, bromobenzene, anisole, benzonitrile, benzofuran,2-bromobiphenyl, 3,3'-dimethylbiphenyl and l-chloronaphthalene.

The mol ratio of total (A) to (B) to total (C) and (D) can be as littleas 0.0001 :1 as taught in the prior art but preferably ranges from0.00l:1 to 0.01 to 1.

For simple polymerization of olefins (C) no aromatic component (D) needbe present, especially for the polymerization of ethylene to a highpolymer, but small amounts of component (D) may accelerate thepolymerization reaction. In such cases the mol ratio of (D) to (C)should be less than 0.01:1, preferably no more than about 0.001:1.

For the alkylation of aromatic compounds (D) the mol ratio of (C) to (D)is generally about the same as the desired degree of substitutiondesired. If 1 mol of (C) is desired to react with 1 mol of (D), theultimate mol ratio of(C) to (D) will be 1:1. [f2 mols of (C) are desiredto react with 1 mol of (D), the ultimate mol ratio of (C) to (D) will be2:1. With the thoroughly reacted catalyst combination of this inventionthe alkylation reaction of (C) and (D) takes place in preference topolymerization of the olefin (C) unless there is a large excess of (C)compounds compared to the available reactive sites on the compounds of(D).

The temperatures required for the alkylation and/or polymerizationreactions with the catalyst combinations of this invention are notparticularly critical with the catalyst combinations of this invention.Some heat may be necessary to initiate reactions such as heating to atleast 30C. The maximum temperature which can be employed is dependent onthe melting points, boiling points and decomposition points of thecatalytic components (A) and (B), the reacting components (C) and (D)and the products as well as the desired control over rate of reaction.For practical purposes, the maximum temperature is about 200C. and thepreferred temperature range is 40 to C.

Ambient pressures are satisfactory generally ranging from atmosphericpressure to no more than about 50 atmospheres, preferably no more than100 psig.

Under these conditions of temperature and pressure either thepolymerization or alkylation reactions can be operated batchwise forfrom 5 minutes to 4 hours or more or these reactions can be runcontinually, especially where the products are in a different physicalstate than the reactants making possible continuous adhigher molecularweight than the reactants so that it can be precipitated out by coolingor other technique or can be selectively distilled.

Typically, for polymerization a reaction vessel is purged with somemonomer (C) if gaseous or an inert gas such as nitrogen. Then enough ofthe alkyl aluminum halide (B) is added to dry the vessel. An inertsolvent such as heptane may be added. The desired amount of components(A) and (B) are added, preferably in a mo] ratio of 1:8 to 1:12, withmonomer at ambient pressure at a sufficient rate to allow continuousreaction but not at such an excessive rate as to kill the reaction.Solid product is allowed to settle and is filtered off.

For alkylation the procedure is the same except that the desiredaromatic compound (D) is added to the reaction vessel prior to adding(C).

The following examples are illustrative of the best presently-knownmethods of practicing this invention and are not intended to limit thisinvention the scope of which is delineated in the appended claims.Unless otherwise stated, all quantitative measurements are by weight.

EXAMPLE 1 Preparation of Chromium (lll) Tris (diethyl orthophosphate) Amixture of 50.0 grams chrome alum CrK(SO 12 B (0.10 mole) and 33.0 gramsof magnesium bis (diethyl orthophosphate) Mg [OP (0) (OEt) (0.10

moles) was mixed with 20 ml. of water, evolving heat of reaction to warmthe mixture from 20 to 35C. To this reaction product was added 10 ml.more water and 250 ml. benzene, and the mixture was heated to refluxwhile stirring vigorously for 1 hour. The water phase was allowed tosettle, and the green benzene phase was decanted and filtered, yieldingupon evaporation 28.2 grams of green, brittle glassy material.

Analysis of the unpurified material indicated 10.8% by weight trivalentchromium (theoretical 10.2 wt. percent): This product decomposed withoutmelting upon heating above 250C, but readily dissolved in polar organicsolvents including methylene chloride or chloroform. Molecular weightmeasured by melting point lowering of camphor was found to be 2850 and2350 at 10% and by weight in camphor respectively. This indicatedpolymeric structures of the formula Cr [OP (0) (GEO- 1 from 4 to 6 unitsper molecule.

EXAMPLE 11 Preparation of Chromium (lll) Tris (di-2-chloroethylorthophosphate) A mixture composed of 11.8 grams magnesium bis(di-2-chloroethyl phosphate) (0.025 mole), 4.44grams of chromicchloridehexahydrate CrCl 6 H O (0.0167

mole) and 15 ml. H O was heated to 50C. The cooled product solution wasextracted with 50 ml. chlorof rm, and evaporation of the chloroformyielded about 1.0 grams bright green resinous material containing thedesired composition. 1

EXAMPLE lll Use of Chromic Tris(di'-2-chloroethy1orthophosphate) forEthylation of Benzene A 2 liter stirred autoclave was purged withethylene gas and was charged with 500 ml. dry benzene and 1.0 gramsethyl aluminum sesquichloride. A solution containing 0.2 gram chromictris (di-2-chloroethyl orthophosphate) catalyst prepared in Example IIwas charged into one addition funnel, and 1.0 gram ethyl aluminumsesquichloride co-catalyst was charged into a separate funnel.

The reactor was pressured to 20'psig. with ethylene gas and maintainedat this pressure throughout the reaction, while the catalyst andco-catalyst were metered into the reactor over a 20-minute period.Reaction temperature of 25C. was maintained constant by external coolingthroughout the -minute reaction period. Analysis of the liquid reactionproduct indicated 25 grams monoethyl benzene was formed during thereaction.

EXAMPLE IV Use of Chromic Tris(diethyl orthophosphate) Propylation ofNaphthalene Into a 2 liter stirred autoclave dried and purgedwithpropylene was charged grams naphthalene (1.0 mole) and 500 ml. ofn-heptane. A catalyst mixture containing 0.344 gram chromic tris(diethylorthophosphate) prepared as in Example I and 1.0 gram ethylaluminum sesquichloride in 15 ml. methylene chloride and 15 ml. benzenewas injected into the reactor. Propylene pressure was maintained around20 psig. while 2.0 grams ethyl aluminum sesquichloride was addedthroughout the reaction to maintain the reaction temperature around 40C.A total of grams (4.3 moles) propylene was completely reacted within 90minutes. Molar percentages of the alkylated naphthalenes as indicated bygas chromatography analysis of the solvent free product were as follows:

Unreacted Naphthalene 6.9% Monoisopropyl Naphthalene 20.9% DiisopropylNaphthalene 10.8% Triisopropyl Naphthalene 20.3% TetraisopropylNaphthalene 13.9%

Penta and Hexaisopropyl Naphthalene 27.0%

About 12 grams of the propylene was converted to trimethyl cyclohexane.The tetraisopropyl naphthalene was found to consist largely of thel,3,5,7, isomer.

EXAMPLE V Use of Chromic. Tris(diethyl orthophosphate) forPolymerization of lsobutylene A source of isobutylene gas at 40 psig.was connected to the autoclave and the exothermic reaction wasmaintained at 50C. for 100 minutes. The light yellow oil reactionproduct weighed 2l38 grams. This product was only slightly soluble inmethanol. Viscosity at 38C. was measured to be 900 centipoise, typicalof low molecular weight polyisobutylene ranging in degree ofpolymerization from 100 to 1000 monomeric units.

EXAMPLE VI Use of Chromic Tris(diethyl orthophosphate) forPolymerization of Ethylene A clean, stirred 2 liter reactor was purgedwith ethylene gas, and 1300 ml. of dry heptane was charged. A solutioncontaining 0.6 gram of chromic tris(diethylorthophosphate) catalyst in40 ml. benzene was charged into one addition funnel. Into a separateaddition funnel was charged 1.2 grams of diethyl aluminum chlorideco-catalyst in 40 ml. of heptane.

Ethylene monomer gas regulated at 30 psig. was connected to the reactorthroughout the course of reaction. Catalyst and co-catalyst were meteredat the same rate into the reactor over a -minute period. During the 2hours following the start of catalyst addition, the reaction exothcrmraised the autoclave from to 45C. The reaction product was filtered torecover solid polyethylene, which was washed with isopropanol and driedand weighed 45 grams. The polyethylene product was typical of highmolecular weight, medium density polyethylene (0.919 grams/cc.) andsoftened above 120C. to a drawable melt.

1 claim:

1. A compound soluble in halogenoalkane solvents and having the formulaCr [OP (0) (OR) in which each R is selected from the class consisting ofalkyl, cycloalkyl, alkoxyalkyl, chlorinated derivatives thereof andbrominated derivatives thereof, said alkyl and cycloalkyl containing oneto eight carbon atoms and said LII alkoxyalkyl containing three to sixcarbon atoms.

2. The method consisting essentially of l) heating a compound of theformula M [OP (0) (OR) in which M in an alkali metal or alkaline earthmetal, 11 is the valence of that metal and each R is selected from theclass consisting of alkyl, cycloalkyl, alkoxyalkyl, chlorinatedderivatives thereof and brominated derivatives thereof, said alkyl andcycloalkyl containing one to eight carbon atoms and said alkoxyalkylcontaining three to six carbon atoms, with a compound of the formulaM,,Z,, in which each M is trivalent chromium, each Z is a non-reducingsubstituent selected from the group consisting of anions of non-metallicinorganic acids, the hydroxyl group and organic carboxylic groups offrom one to about 18 carbon atoms, a is l or 2, b is l or 3 and thevalues of a and b depend on the valence of Z, said heating being at atemperature between about 0 and C. but below the decompositiontemperatures of the reactants and at a pressure and for a timesufficient to cause a reaction, and (2) separating from the reactionmixture a product consisting essentially of a compound soluble inhalogeno-alkane solvents and having the formula Cr [OP (0) (OR) byextraction with a solvent for said product but not for the resultingM-containing by-product.

3. A composition in accordance with claim 1 wherein each R is an alkylgroup of two to four carbon atoms.

4. A composition in accordance with claim 1 wherein each R is analkoxyalkyl group containing three to six carbon atoms.

5. A method in accordance with claim 2 wherein each R is an alkyl groupof two to four carbon atoms.

6. A method in accordance with claim 2 wherein each R is an alkoxyalkylgroup containing three to six carbon atoms.

7. A method in accordance with claim 2 wherein each M is an alkalineearth metal.

1. A COMPOUND SOLUBLE IN HALOGENALKANE SOLVENTS AND HAVING THE FORMULACR (OP (O) (OR)2)3 IN WHICH EACH R IS SELECTED FROM THE GROUP CONSISTINGOF ALKYL CYCLOALKYL, ALKOXYAKYL, CHLORINATED DERIVATES THEREOF ANDBROMINATED DERIVATIVES THEREOF, SAID ALKYL AND CYCLOAKYL CONTAINING ONETO EIGHT CARBON ATOMS AND SAID ALKOXYALKYL CONTAINING THREE TO SIXCARBON ATOMS.
 2. THE METHOD CONSISTING ESSENTIALLY OF(1) HEATING ACOMPOUND OF THE FORMULA M'' (OP (O) (OR)2)N IN WHICH M'' IN AN ALKALIMETAL OR ALKALINE EARTH METAL, N IS THE VALENCE OF THAT METAL AND EACH RIS SELECTED FROM THE CLASS CONSISTING OF ALKYL, CYLOAKYL, ALKOXYL,CHLORINATED DERIVATIVES THEREOF AND BROMINATED DERIVATIVES THEREOF, SAIDALKYL AND CYCLOAKYL CONTAINING ONE TO EIGHT CARBON ATOMS AND SAIDALKOXYALKYL CONTAINING THREE TO SIX CARBON ATOMS, WITH A COMPOUND OF THEFORMULA MAZB IN WHICH EACH M IS TRIVALENT CHROMIUM, EACH Z IS ANON-REDUCING SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF ANIONS OFNON-METALLIC INORGANIC ACIDS, THE HYDROXYL GROUP AND ORGANIC CARBOXYLICGROUPS OF FROM ONE TO ABOUT 18 CARBON ATOMS, A IS 1 TO 2, B IS 1 OR 3AND THE VALUES OF A AND B DEPENDEND ON THE VALENCE OF Z, SAID HEATINGBEING AT A TEMPERATURE BETWEEN ABOUT 0* AND 150*C. BUT BELOW THEDECOMPOSITITION TEMPERATURES OF THE REACTANTS AND AT A PRESSURE AND FORA TIME SUFFICIENT TO CAUSE A REACTION, AND (2) SEPARATING FROM THEREACTION MIXTURE A PRODUCT CONSISTING ESSENTIALLY OF A COMPOUND SOLUBLEIN HALOGENO-ALKANE SOLVENTS AND HAVING THE FORMULA CR (OP (O) (OR)2)3 BYEXTRACTION WITH A SOLVENT FOR SAID PRODUCT BUT NOT THE RESULTINGM''-CONTAINING BY-PRODUCT
 3. A composition in accordance with claim 1wherein each R is an alkyl group of two to four carbon atoms.
 4. Acomposition in accordance with claim 1 wherein each R is an alkoxyalkylgroup containing three to six carbon atoms.
 5. A method in accordancewith claim 2 wherein each R is an alkyl group of two to four carbonatoms.
 6. A method in accordance with claim 2 wherein each R is analkoxyalkyl group containing three to six carbon atoms.
 7. A method inaccordance with claim 2 wherein each M'' is an alkaline earth metal.